卡林型金矿金砷成分分析标准物质研制

卡林型金矿因其含砷影响金的分析和选冶回收率而备受关注,需要研制相应的标准物质支撑应用研究。本文依托近年来探明的超大型卡林型金矿——阳山金矿采集候选物,按照国家一级标准物质技术规范研制了4种卡林型金矿标准物质GBW07854~GBW07857。共有20家实验室联合定值,金主要分析方法为原子吸收光谱法和火试金法,湿法分析采用梯度焙烧-活性炭吸附金而分离砷等干扰组分;砷分析主要采用电感耦合等离子体发射光谱法和分光光度法。引用金量分析相对偏差允许限界定组内离群值,弥补了Dixon法和Grubbs法剔除离群值不够完全的缺陷。均匀性检验指标FF0.05(29,30)=1.84,表明组内和组间均无明显差异;在22个月内进行了5次检验,稳定性良好。4种标准物质金和砷的定值结果准确度均优于同量级的国家一级金矿石标准物质和国外含砷多金属矿石标准物质。该系列标准物质可用作卡林型金矿金和砷分析与研究等工作的量值标准。     

痕量金及金矿石标准物质复制

1986年至2007年期间,中国先后研制了适用于区域地球化学调查、矿产勘查与评价、采矿与选冶等不同工作需求的背景、异常、中等、高含量以及矿化、边界品位、精矿等不同品级的痕量金和矿石金系列标准物质。经过多年使用尤其是近年来使用量的递增,这些标准物质中多数样品已经或已近耗尽,急需研制替代的标准物质。2016—2018年,本文严格按照国家一级标准物质研制的相关规范,开展了7个痕量金(GBW07805、GBW07806、GBW07243～GBW07247)和3个矿石金[GBW(E)070012、GBW07807、GBW07299]地球化学标准物质的复制工作。在全国范围内选采了矿床和介质类型具有代表性的候选物,经粗碎、烘干、组合配置、细碎、过筛、混匀等步骤制备而成。经粒度检查,样品粒径达到0.74μm的累计含量达到99%以上,符合规范要求。本系列标准物质采用电感耦合等离子体质谱法(ICP-MS)、火焰原子吸收光谱法(FAAS)及石墨炉原子吸收光谱法(GFAAS)等经典可靠的分析方法测定金含量,每个样品随机抽取25瓶子样进行均匀性检验测试,相对标准偏差(RSD)均都小于10%,方差检验的F值均小于单尾临界值F_(0.05(24,25))=1.98,表明样品均匀性良好。在一年的考察期内,定值成分未发现统计学意义上的明显变化,证明样品的稳定性良好。由中国5家具有金测试经验、技术力量强的实验室,采用经典可靠的多种测试方法共提供了292组分析数据完成定值测试。原始数据经统计检验并剔除可疑值后符合正态分布,以算术平均值作为标准值,并按照最新规范详细评定了不确定度。复制的标准物质量值准确可靠,不确定度合理。与原批次相比,两个批次的认定值基本一致,定值数据的标准偏差呈缩小趋势,符合标准物质复制的要求。本系列金标准物质含量范围广,适用于不同含量级次的量值比对和分析监控,可以满足地质矿产研究、区域地球化学调查、金矿勘查与评价的需要。     

高演化烃源岩岩石热解和总有机碳标准物质研制

南方下古生界海相页岩是我国页岩气勘探开发的重点地层,普遍具有时代老,热演化程度高的地质特征。已有基于常规测试条件制备的岩石热解及总有机碳分析标准物质无法满足此类高演化样品分析的需求,一定程度上制约了页岩气勘探开发进度。研究采集贵州织金龙潭组的泥岩及煤样,按照国家一级标准物质研制标准和规范,研制2件高演化烃源岩标准物质(编号为GBW07499和GBW07500),定值指标S2、 T max和TOC。经均匀性检验,三个指标的F值均小于临界值F0. 05(v1, v2),样品单元间均无显著性差异,均匀性良好。经两年时间考察室温条件下特性量值S 2、 T max和TOC的变化趋势,结果表明拟合直线斜率b 1＜t 0. 05. S(b 1),稳定性良好。经多家权威实验室联合定值, 全部定值分析数据符合正态和近似正态分布,且等精度,给出认定值和不确定度分别为：S 2为1. 09±0. 10mg/g, T max为633±3℃,TOC为26. 8%±1. 3%;S 2为6. 31±0. 48mg/g, T max为613±4℃,TOC为63. 1%±3. 4%。2件标准物质可满足高演化样品岩石热解和总有机碳分析测试工作的需求,为解决该类样品分析过程中仪器校准、方法评价和数据质量监控等问题提供物质基础,有效提升测试数据质量。     

黑色页岩样品中痕量级铂族元素地球化学成分标准物质研制

介绍了黑色页岩样品中6个铂族元素铂、钯、钌、锇、铑、铱的标准物质研制过程。黑色页岩样品采自贵州黄家湾,为一次采集、一次混样的原始样品,随机抽取包装好后的样品进行检验与定值。均匀性、稳定性符合要求后,按照国际标准化组织(ISO)34、35指南的基本要求和我国一级标准物质的技术规范,采用多个实验室协同测试的定值方式,利用不同原理的分析方法对此样品的6个铂族元素进行定值。以各实验室组数据作为最小统计单元,用Grubbs准则、Dixon法检验剔除离群数据,Shapiro-Wilk法检验各元素数据分布的正态性。检验结果100%的元素呈正态或近似正态分布。定值的6个元素均符合标准值水平。     

金银地质标准样品的研究概况及其测试方法的讨论和应用

本文评述了金银地质标样的研制概况及其分析方法的应用。第一部分汇总了我国和世界金银地质标样的研制情况,只有少数样品的金银含量有了审定值。第二部分讨论了金和银的测试方法,较详细地讨论了古典火试金、容量法和化学富集原子吸收法的对比及应用。     

松花江哈尔滨段水系沉积物中无机元素环境标准样品的研制

介绍了松花江哈尔滨段水系沉积物环境标准样品的研制方法,对其中21个无机元素进行定值。采集的水系沉积物样品经自然阴干、研磨、筛分、混匀、装瓶和灭菌等加工处理后,分层随机抽取18瓶样品,在0.25 g样品取样量条件下,以铜、铅、锌、砷、汞、铁和铝为代表元素进行均匀性研究,结果表明样品均匀性良好。在室温避光保存条件下,以铜、铅、锌、砷和汞为代表元素,采用线性模型进行稳定性研究,在15个月研制期间样品未观察到不稳定性。由11家协作实验室对水系沉积物标准样品中的21个无机元素进行定值研究,经统计检验分析评定出20个元素的标准值和不确定度,1个元素给出参考值。研制成的标准样品已应用于土壤或水系沉积物样品中无机元素的监测。     

珠江三角洲沉积物标准物质研制

为满足近海地球化学调查及资源勘探的需要,研制了3个珠江三角洲沉积物标准物质.样品经干燥、球磨至200目,采用XRF法进行均匀性检验,结果显示方差检验的F实测值均小于列表临界值,证明样品具有较好的均匀性.在2年时间内选取有代表性的元素进行了4次稳定性测试,结果表明样品稳定性良好.共12家实验室参加了合作定值,采用了16种准确可靠的分析方法,最终定值元素70项.该标准物质的研制将为河口三角洲地区地质调查提供可靠的质量保证.     

火焰原子吸收光谱法测定高品位金矿石中的金

采用经典火试金法测定高品位金,操作流程长,影响因素多,在铅扣灰吹过程中易挥发选出大量的铅,对实验环境造成严重污染.本文将20.0～100.0 g取样量先分成若干小样量进行焙烧,经50％王水完全分解后分离滤渣,所得若干份滤液定容于同一容量瓶内,分取适量体积进行泡沫塑料富集,将富集金的泡沫塑料灰化后用浓王水复溶,以火焰原子吸收光谱法(FAAS)测定高品位金矿石中金的含量.方法检出限为0.101 μg/g,通过多个国家一级标准物质和分析样品验证,准确度和精密度满足相关要求.此方法测定灵敏度高,取样量为20.0 ～ 100.0 g,有效地提高FAAS法取样代表性,同时拓展了FAAS法测定矿石中金的含量范围,针对50.0 ～ 550.0 μg/g中高含量段的金结果同样可靠.     

二苯硫脲泡塑富集-原子吸收光谱法连续测定化探样品中金和银

传统的发射光谱、化学光谱、泡塑富集分离-原子吸收光谱法测定化探样品中的金和银,分析结果不稳定,效率低。本研究提出用50%的王水分解化探样品,负载二苯硫脲泡塑吸附金银,石墨炉和火焰原子吸收光谱法对金和银进行联合测定。在二苯硫脲浓度、吸附酸度、吸附温度、振荡时间等优化的实验条件下,金和银的回收率分别达到97.9%和98.8%,检出限为0.25 ng/g和0.038μg/g,准确度(RE,n=9)为2.0%～14.0%和7.7%～13.3%,精密度(RSD,n=9)为3.1%～12.4%和5.1%～13.2%。经国家标准物质分析验证,测定值与标准值基本相符。该方法实现了在同一份溶液中同时测定金和银,与现行的石墨炉原子吸收光谱测定金、发射光谱测定银的方法相比,称样量达到10 g,样品的代表性显著增加,提高了准确度和精密度,简化了金银分析的程序,化学试剂用量少,分析成本低。     

四川石棉县大水沟碲多金属矿床辉碲铋矿研究

四川石棉县大水沟碲多金属矿床是一个以碲为主的矿床。在该矿床中,辉碲铋矿作为一种最主要成矿矿物而大量堆积。化学分析和X射线粉晶衍射测试表明其为标准的辉碲铋矿,晶胞参数a=4.1408-4.5225,c=29.5008-29.6170.铋含量为57.65%-58.68%,碲35.20%-36.4%和硫4.5%-5.36%.另外,辉碲铋矿含有较多的杂质元素铁、铅、硒、锑、金和银,其中硒、金和银含量分别达1600-2600g/t,1.4-10.7g/t和2300-3400g/t.辉碲铋矿的δ³⁴S的变化范围示意出硫来源于地幔。其矿床成因可能与岩浆活动有关。     

Comparison of Silver and Gold Inquarting in the Fire Assay Determination of Palladium/Platinum and Rhodium in Geological Samples

The classical lead fire assay is still the most important method for the pre-concentration and separation of Ag, Au and some of the platinum-group elements (PGE) in the analysis of geological materials. The most frequently used fire assay procedure is the determination of Au, Pd and Pt with Ag as collector. When Au is used instead of Ag as a collector, Pd, Pt, Rh and possibly Ir can also be determined. In this study the recoveries by Au and Ag collectors, also called inquarts, were compared in the fire assay analysis of Pd, Pt and Rh in geological reference materials. The amount of gold to be added was optimised. Variable recoveries were obtained with Ag inquart for Rh, but a 2 mg inquart of Au gave good recoveries for all three of these elements in the analysis of reference samples of different geological materials. A procedure, alternative to scorification, to overcome interferences caused by base metals in the cupellation step is presented. The procedure involves cutting the Pb button into pieces and analysing the pieces separately. Prior to this, a homogeneity study of the lead button was made, and it showed that Pd, Pt and Rh were evenly distributed in the Pb button. All determinations were made using inductively coupled plasma-atomic emission spectrometry (ICP-AES).     

Comparison of Recoveries by Lead Fire Assay and Nickel Sulfide Fire Assay in the Determination of Gold/ Platinum/ Palladium and Rhenium in Sulfide Ore Samples

We compared the recovery of gold, palladium and platinum by two fire assaying procedures, using nickel sulfide and lead as collectors. The presence of appreciable amounts of sulfide minerals in the sample caused interferences in both procedures. An in-house reference sample, a reference sample of high-grade sulfide ore and samples of high sulfide content from the Recsk porphyry copper ore in Hungary were analysed by both methods. The elements were determined by inductively coupled plasma-atomic emission (ICP-AES) and/or inductively coupled plasma-mass spectrometry (ICP-MS). It was found that for the sulfide ore samples, the recoveries of Au and Pd are sometimes lower by nickel sulfide fire assay than by lead fire assay. Recovery of Re by nickel sulfide fire assay was found to be low: the average recovery of five repeated analyses of the reference sample NIST SRM 330 was 9% with a relative standard deviation of 48%. Increasing the amount of S in the fusion flux gave better recovery.     

Visible and “invisible” forms of gold and silver in the crystallization products of melts in the Fe–S–Ag–Au system: experimental data

The forms of Au and Ag occurrence in the crystallization products of melts in the Fe–S–Ag–Au system depending on the proportions of Fe/S and Ag/Au have been studied at (Fe + S)/(Ag + Au) = 0.1. It is shown that the S-rich systems with S/Fe = 2 contain Au–Ag sulfides and Au–Ag alloys. The systems depleted in S with S/Fe = 1 contain only Au–Ag alloys. The results of XPS provide evidence for the sulfide and metallic components of Au and Ag among the crystallization products of melts in the system studied at S/Fe = 2 and a metallic component with S/Fe = 1. According to the data of electron microprobe analysis, the content of “invisible” forms of noble metals in pyrite and pyrrhotite is < 0.024 wt % for Au and <0.030 wt % for Ag; the contents of “invisible” Au and Ag in troilites are 0.040 ± 0.013 wt % Au and 0.079 ± 0.016 wt % Ag.     

Bias in the analysis of geological materials for gold using current methods

A consistent pattern has been observed in the results obtained for Au in three soil and two porphyry copper ore samples serving as control reference standards in geochemical analyses. The mean reported by wet chemical methods (regardless of the measurement technique) was less than the mean by fire assay-based methods which, in turn, was less than the mean reported by laboratories using direct instrumental neutron activation analysis (INAA). These data have been obtained from 16 laboratories, some employing more than one method. Compared to INAA, values obtained for Au (at the 30–300 ppb level) using aqua regia (AR) dissolution were low by 24–42%, while those reported by fire assay-based methods were low by 14–26%.Studies of these samples and 32 rocks of widely varying composition revealed that the amount of Au remaining in the residue after AR attack ranged from 4% to 59% of the total. Gold dissolved by AR was determined by graphite furnace atomic absorption spectrometry (GFAAS) after extraction into MIBK (methyl isobutyl ketone), whereas Au remaining in the residue was determined by INAA. The slope of the line obtained by plotting Au by INAA vs. the sum of Au by AR/GFAAS and Au in the residue was not significantly different from 1.0.Modifications to the AR procedure such as prior attack by HCl or HF did not improve the recovery of Au in the three reference soils. However, reduction of sample size from 10 g to 1 g while maintaining the volume of AR at about 30 ml did increase results for Au. Furthermore, addition of HF in the attack on 1-g samples yielded results virtually identical to those obtained by INAA. It is thought that the poor extraction efficiency by AR is due to non-wetting of the larger sized sample, a lack of intimate, prolonged contact between the grains of the sample and the acid mixture and the presence of insoluble gangue surrounding Au particles. Constant agitation of the sample during evaporation with AR is desirable.The mean values obtained for Au in the soils by fire assay methods were not significantly different from the results by INAA (low by 14–19%); this was not the case for the two copper ore samples (low by 26%). This probably reflects the difficulties encountered in fire assay by high concentrations of Cu which hinder effective collection and separation of Au into the Pb button. However, the accuracy of the INAA method has not been established and is dependent upon measurement procedures and the degree of certainty associated with the Au values assumed for the reference materials employed for calibration. While estimation of precision does not present a problem, accuracy is difficult to assess in the absence of certified reference materials for Au at concentrations in the 10–300 ppb range. However, it is concluded that methods based upon AR dissolution can lead to low results, the magnitude being dependent upon the sample matrix and the mineralogical association of the Au present.     

西藏地堡那木岗矿区水系沉积物地球化学特征及找矿预测

利用SPSS等软件对矿区1：5万水系沉积物地球化学数据分析,选用平均值±3倍标准差（X±3S）作为上下限反复剔除原始数据的特值,使元素含量服从正态分布.最后以X+2S作为异常下限（T）,以1T、2T、4T三级浓度分带,圈定Cu、Au、Ag、Mo单元素异常和Au-Ag-Mo综合元素异常,揭示矿区内水系沉积物地球化学异常特征.将异常区与矿区地质特征、矿床（点）套合分析,表明异常受地层、断裂、围岩蚀变控制,对寻找矿（化）体、断层、围岩蚀变带有指示作用.最终,优选2处远景区,分别为3号综合异常区中心北北西方向至北东向断裂附近,1号、2号综合异常区及其东侧组成一个走向为东西向的异常带.     

Trace Element Analysis of Natural Gold by Laser Ablation ICP-MS: A Combined External/Internal Standardisation Approach

For the trace element analysis of gold by laser ablation ICP-MS, external calibration samples of differing matrix composition have been used in previous studies. Data presented here suggest that even for calibration samples and unknowns with closely-matched matrices, discrepancies arise due to variations in the coupling behaviour of the laser with the sample at different power deliveries, and can lead to erroneous trace element determinations. Internal standardisation for gold is complicated because Au and Ag, the most common major elements, do not have minor isotopes that can be used as internal standards. This problem was overcome for natural gold samples by using an external calibration sample only for the major elements Au and Ag, then defocussing the ion path and using ¹⁰⁷Ag in each sample as an internal standard against which μg g^-1 levels of Te, Sb, Hg, Bi, and Cu were determined. The results suggest that trace elements can occupy lattice sites in gold rather than occurring only as micro-inclusions of other phases. The analytical approach taken here may be used in trace element analysis where adequate external calibration samples are not readily available.     

混合吸附剂分离富集-电感耦合等离子体质谱法测定地质样品中铂钯金

贵金属分析应用火试金法分离富集时,试金配料复杂、耗时较长,分析成本相对较高,空白较难控制.本文建立了采用过氧化氢-盐酸湿法分解样品,电感耦合等离子体质谱同时测定地质样品中Pt、Pd、Au的分析方法.在10％的盐酸介质中,以LSC-400巯基树脂和活性炭为混合吸附剂,采用动态吸附方式对样品中的Pt、Pd、Au分离富集,用Lu作内标元素,195 Pt、197 Au、108 Pd为待测同位素消除了非谱线干扰和谱线干扰,三元素的回收率均大于96.4％.方法检出限(3σ):Pt为0.06 ng/g,Pd为0.08 ng/g,Au为0.12 ng/g,优于火试金等其他分离富集方法的检出限.应用于测定国家标准物质,Pt、Pd、Au的测定结果与标准值相符,12次测定的相对标准偏差均小于16.1％,满足区域地球化学调查样品的分析要求.该方法操作简便、成本低廉,提高了分析速度,有效地降低了测试过程的空白值.     

含铜、铋和银的金精矿堆浸工艺综合回收试验研究

采用生物氧化技术和化学方法,利用堆浸工艺分步提取,对含Au 140~150 g/t、Ag 900~1 000 g/t、B i 9.0%~10.0%、Cu14%~17%的多金属浮选金精矿的综合回收工艺进行了研究。经小型搅拌试验,确定了生物氧化浸铜—氰化浸金、NaC l-FeC l3-HC l体系(氯盐法)浸出铋和银的技术方法。通过柱浸试验,研究了利用该方法分步浸取Au、Ag、Cu和B i在堆浸工艺中的可行性。在10 t精矿的扩大试验验中,验证了柱浸试验所取得的工艺指标和参数。试验中掺入骨架材料,解决了精矿在堆浸中的渗透问题;生物氧化过程中,菌种在含高浓度铜离子浸出液中反复驯化,对铜的耐受力提高到30 g/L;在NaC l-FeC l3-HC l体系浸出B i和Ag时,用H2O2将浸出液中的Fe2+氧化成Fe3+,使浸出液能循环使用,且B i和Ag同时浸出。Au、Ag、Cu和B i的最终浸出率分别为92.98%、65.09%、45.33%和53.49%。     

阴离子树脂-活性炭分离富集等离子体发射光谱法测定富钴锰结壳中的痕量金银铂钯

采用717阴离子树脂活性炭联合交换分离富集技术,电感耦合等离子体发射光谱法同时测定富钴锰结壳中痕量金、银、铂、钯。方法检出限四元素分别为:Au1. 3、Ag0. 4、Pd0. 6、Pt4. 8ng/g。样品加标回收率在89. 0% ~110. 3%,相对标准偏差3. 5% ~7. 8% (n=4)。方法已用于富钴锰结壳中痕量金银铂钯的测定。     

NK8310螯合树脂分离富集地质样品中痕量金银铂钯及其测定

研究了硫脲螯合树脂（NK8310）分类富集地质样品中痕量Au、Ag、Pt和Pd的实验条件。在φ=10％的王水介质中，[AuCI4]^-、[AgCI2]^-、[PtCI6]^2-和[PdCI4]^2-定量吸附于树脂上并与大量贱金属分离；用5g/L硫脲－0.12mol/L HCI溶液洗脱Au、Ag、Pt和Pd，回收率为97％－104％。用硫镍矿管理样以及国家一级标准物质进行分析验证，分析结果与推荐值及标准值吻合，表明NK8310螯合树脂适用于地质样品中Au、Ag、Pt和Pd的分离富集。